Non-ionized cyanine dyes



NON-IONIZED CYANINE mus Leslie G. S. Brooker and Frank L. White, Rochester; N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation New Jersey No Drawing. Application August 19, 1953,

Serial No. 375,279

12 Claims. (Cl. 260-240.1)

This invention relates to non-ionized dyes, and in particular, trinuclear dyes which. contain no acidv anion, such as iodide, chloride, etc.

This application is a continuation-in-part of our application Serial No. 282,696, filed April 16, 1952 (now abandoned).

Trinuclear dyes of the cyanine type have long been known and more recently cyanine dyes of the carbocyanine type having a pyrazolyl group in ,the mesa-position have been described. See, for example, Kendall and Fry U. S. Patent 2,385,815, issued October 2, 1945,.

We have now found a new class of cyanine dyes which can advantageously be used as optical sensitizers for photographic silver halide emulsions. The new cyanine dyes of our invention do not contain the conventional acid anions, such as chloride, iodide, etc. and we have accordingly designated these new dyes as non-ionized dyes. These new dyes cannot be precipitated by the usual 'anions.

The new non-ionized dyes of our invention can be represented by the following general formula:

rtes Paten 2,739,964 Patented Mar. 27, 1956 allylrhodanine, etc.) or S-aryIrhodanines- (e. g. 3-phenylrhodanine;ietc.), (e. g. 3-alkyl-2,4-dithio-2,4-thiazolidinediones), such as 3-ethyl-2,4-dithio-2,4-thiazolidinedione, etc.), those of the 2(3H)-imidazo[l,2-u]pyridone seriesjthose of the 5.7-dioXo-6,7-dihydro--thiazolo[3,2 odpyrimidine series (e. g.. 5,7-dioXo-3-phenyl-6,7-'dihydro-5-thiazolo- 3,2-04 pyrimidine, etc.), those of the 2-thio-2,4-oxazolidine: dione series' (i. e. those of the 2-thio-2,4(3H,5H')- oxazoledione series) "(e. g. 3-ethyl2-thio-2,4-oxazoli= dinedione etc.), those of the thianaphthenone series (e. g;

3(2H-thianaphthenone, etc.), those of the 2-thio.-2,5-, e. the 2-thio-2,5(3H,5H)-' thiazolidinedione series (i. thiazoledione' series) (e. a g. 3rethyl-2-thio-2,S-thiazolidinedione, etc.), etc.', 11, d and In each represents a positive integer of from 1 to 2, and Z and 21- each represents the non-metallic atoms necessary to complete a hetero-' cyclic nucleus containing from 5 to 6 atoms in the heterocyclic ing'of those of the thiazole series (e. g. thiazole, 4- methylthiazole, S-methylthiazole, 4-phenylthiazole, 5- phenylthiazole, 4,5-dimethylthiazole, 4,5-dipheny1thiazole, 4- 2-thienyl)thiazole, etc.), those of the benzothia-;

zole series (e. g. benzothiazole, .4-chlorobenzothiazole,

S-chlorobenzothiazole, 6-chl0robenzothiazole, 7-chloro benzothiazole, 4-methylbenzothiazole, 5-methylbenzo. thiazole, 6.-methylbenzothiazole, 5-bromobenzothiazole,

o-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenyl-l benzothiazole, 4-methoxybenzothiazole;z imethoxybenzo-z thiazole, 6 -methoxybenzothiazole, S-iodobenzothiazole, 6-,, iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzo-- thiazole, tetrahydrobenzothiazole,5,6-dimethoxybenzothia zole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), those of the naphthothiazole series (e. g. a-naphthothiazole, p-naphwherein R and R1 each represents an alkyl group, i. e. an alcohol radical, e. g. methyl, ethyl, n-propyl, n-butyl isobutyl, n-arnyl, isoamyl, ,B-hydroxyethyl, y-hydroxypropyl, fl-methoxyethyl, S-ethoxyethyl, allyl, benzyl (phenylmethyl), fi-phenylethyl, S-carboxyethyl, carboxymethyl, a-carboxyethyl, 'ycarboxypropyl, fl-acetoxyethyl, 'y-acetoxypropyl, carbomethoxyrnethyl, ,B-carbomethoxyethyl, carbethoxymethyl, p-carbethoxyethyl, etc., A represents a sulfur atom or an oxygen atom, Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6- atoms in the heterocyclic ring, such as those of the pyrazolone series (e, g. 3-methyl-l-phenyl-S-pyrazolone, l-phenyl-S-pyrazolone, 1-(Z-benzothiazolyl-S-rnethyl-5-pyrazolone, etc.,), those of the isoxazolone series (e. g. 3-phenyl-5-(4H)- isoxazolone, 3-rnethyl-5-(4H)-isoxazolone, etc.), those of the indandione series (e. g. 1,3-diketohydrindene,etc.), those of the oxindole series, (e. g. l-alkyl-2,3-dihydro-2- oxindoles, etc.), those of the 2,4,6-triketohexahydropyrimidine series (c. g. barbituric acid or Z-thiobarbituric acid as well as their l-alkyl (e. g. l-methyl, l-ethyl, 1- n-propyl, l-n-heptyl, etc.), or 1,3-dialkyl (e. g. 1,3-dimethyl, 1,3-diethyl, 1,3-di-n-propyl, 1,3-diisopropy1, 1,3- dicyclohexyl, 1,3-di(,8-methoxyethyl), etc.), or 1,3- diaryl (e. g. 1,3-diphenyl, 1,3-di(p-chlorophenyl), 1,3- di(p-ethoxycarbonylphenyl), etc.), or l-aryl (e. g. 1 phenyl, l-p-chlorophenyl, l-p-ethoxycarbonylphenyl), etc.) or 1-alkyl-3-aryl (e. g. l-ethyl3-phenyl, l-n-heptyl- 3-phenyl, etc.) derivatives, those of the rhodanine series i. e. 2-thio-2,4-thiazolidinedione series) such as rhodanine, 3-alkylrhodanines (e. g. 3-ethylrhodanine,. v3-

8- methylquinoline,

etc.), those of the g. 4 v methoxythit maphazole, 5 ethoxybenz o azole, 6 chlorobenzoxazole, S-hydroxybenzoxazole, 6.- hydroxybenzoxazole, etc.),. u-naphthoxazole, t

those of the naphthoxazoleseries '(e. g. fi-naphthoxazole, etc.), those of the selenazole series (e. g. 4-methylselenazole,4-phenylselenazole, etc.), those of the benzoselenazole series (.e g. benzoselenazole, 5- chlorobenzoselenazole, 5 methoxybenzoselenazole, 5 hydroxybenaoselenazole, tetrahydrobenzose 1 e n a z 01 e naphthoselenazole series (e. g. anaphthoselenazole, fi-naphthoselenazole, etc.), those .of the thiazoline series (e. g. thiazoline, 4-methylthiazoline, etc.), those of. the 2-quinoline series methylquinoline, S-methylquinoline,

6 methoxyquinoline, 6- ethoxyquinoline, 6 hydroxy= quinoline, 8-hydroxyquinoline, etc.), those of the 4- quinoline series (e. g. quinoline, 6-methoxyquinoline, 7 methylquinoline, 8-methylquinoline, etc.), those of the l-isoquinoline series (e. g. isoquinoline 3,4-dihydrisoetc., those of the-thiorhodanineseries ring, such as those selected from the group consistthose of thethionaphthenq (e. g. quinoline, 3- 7methylquinoline,, 6-chloroquinoline, 8-chloroquinoline,,-

' an aryl group (e. g. phenyl,

. J quinoline etc.), those of the 3,3-dialkylindolenine series (e. g. 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), those of the 2-pyridine series (e. g. pyridine, 3-methylpyridine, 4-methylpyr'idine,

' S-methylpyridine, 6 methylpyridine, 3,4 dimethylpyriother object is to provide a method of making such photographic silver halide emulsions. Other objects will become apparent from a consideration of the following description and examples.

According to our inventionwe provide thenew nonionized dyes represented by Formula I above wherein d represents 1 by reacting a merocarbocyanine dye selected from those represented by the following generalformula:

wherein R, A, Q, n and Z each have the values given above, with a cyclammonium quaternary salt selected from those represented by the following general formula: 7

III. zr

R1if oH-o11),.IlE-sar wherein R1, m and Z1 each have the values given above, R2 represents an alkyl group (e. g. methyl, ethyl, etc) or m and p-tolyl, etc.), and

X represents an acid anion, e. g. chloride, bromide, iodide,

thiocyanate, sulfamate, methyl sulfate, ethyl sulfate, per

chlorate, -p-toluenesulfonate, etc.

The condensations can be accelerated by heating; and generally, temperatures varying from room temperature to about reflux temperature of the reaction mixture can be'used. The condensations can also be carried out in the presence of an inert solvent", such as pyridine, quinoline, isoquinoline, ethanol, n-propanol, n-bu'tanol, etc. Advantageously, the condensations are carried out in the presence of a basic condensing agent, suchas the trialkyl amines (e. g. triethylamine, tri-n-propylamine, tri-n-' butylamine, etc.), N-methylpiperidine, N-ethylpiperidine, N,N-dimethylaniline, etc. The intermediates represented by Formula II above can be prepared as described in Kendall U. S. Patent 2,272,163, Brooker and White U. S. Patents 2,165,338 and 2,263,757; or according to the process described in Kendall U. S. Patent 2,265,908.

The new non-ionized cyanine dyes of our invention represented by Formula I above wherein d represents 2 can be prepared by condensing a merocarbocyanine dye selected from those represented by Formula 11 above with a cyclammonium quaternary salt selected from those represented by the following general formula:

42' wherein R1, m and Z1 each havethe values setforth above, R4 represents an acyl group (e. g. acetyl, propionyl, benzoyl, etc.), Rs represents an aryl group (e. g.

phenyl, o-, mand p-tolyl, etc.), and X2 represents an acid anion, such as those set forth above for X. The condensations can be accelerated by heating the reaction mixture, generally, the temperatures varying from room temperature to the reflux temperature of the reaction mixture. The condensations can be carried out in the presence of an inert solvent, such as pyridine, nitrobenzene, ethanol, n-propanol and n-butanol. Advan- .tageously,'the condensations' are carried out in the presence of a basic condensing agent, such as those set forth above wherein compounds of Formula II are condensed with those of Formula III. l

Alternately, we have found that the new non-ionized cyanine dyes of our invention represented by Formula I wherein d represents 1 can be prepared by condensing a carbocyanme dye selectedtrorn those represented by the following general formula: t

wherein R, R1, n, m, Z and Z1 each have the values set forth above, Ra-represents an alkyl group, (e. g. methyl, ethyl, etc.), or an aryl group (phenyl, o-, m-, and p-. tolyl, etc.), and X1 represents an acid anion, such as those set forth above for X, with a keto-methylene compound selected from those represented by the following general formula wherein Q andA have the values given above. The condensations can be carried out in the presence of an inert solvent, such as pyridine, ethanol, n-propanol, n-butanol, etc., and the condensations can be accelerated by heat.

Generally, temperatures varying from room temperature to the reflux temperature of the reaction mixture canbe used. Advantageously, the condensations are carried out in the presence of a basic condensing agent, such as those set forth above for the condensation of the compounds of Formula II. with those of Formula III.

We have also found that new non-ionized styryl dyes can be prepared by condensing a compound selected from those of Formula II above with an aromatic, aldehyde, such as p-dimethylamino benzaldehyde, p-diethylaminobenzaldehyde, etc. 7

The intermediates selectedfrom those represented by Formula V above can be prepared according to the methods described in Schulz U. S. Patent 2,156,464,. Kendall U. S. Patents 2,397,013 and 2,397,014, and Van de Straete U. S. Patent 2,484,536.

The following examples will serve to illustrate more fully the manner whereby we prepare the new nonionized dyes of our invention.

EXAMPLE I 5- di( 3-ethyl-2 (3H -b enzothiaz0lylidene) isopropy lidene] -1 -mezhyl-2-thiobarbitmic acid A mixture of 1.80 g. (1 moi.) of 5-[ (3-et hyl-2'(3H)-- benzothiazolylidene)isopropylidene] 1 methyl 2-thiobarbituric acid, 5.24-g. (1 m0]. plus 200% excess)" of 2-ethylmercaptobenzothiazole ethoethylsulfate and 1.52 g. (1 mol. plus 200% exceess) of triethylamine in 20 ml. of pyridine was heated at the refluxing temperature for 20 minutes. After cooling to room temperature, the reaction mixture was filtered and the residue was washed first with methyl alcohol and then several portions of pyridine. The residue was dissolved in 30 ml. of pyridine and the solution was chilled and filtered. The pyridine filtrate and all pyridine washings were combined, concentrated and chilled. Then the dye was recrystallized from pyridine. The yield of dye was 54%. The dark green crystals had melting point 327-328 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 645 mu with maximum sensitivity at about 620 mu.

EXAMPLE 2 1,3-aierhyl-5-l (3-ethyl 2(3H) benzothiazolylidene) (1- ethyl 2(1H) ,8 naphthothiazolylidene)isopropylideneJZ-thiobarbituric acid g. (1 mol.) of 1,3-diethyl-5-[(1- EXAMPLE 3 4-[di(1-ethyl 2(1H) B naphthothiazolylidene)isopropylidene] -3-'phenyl-5 (4H -isxaz0lone A mixture of 1.37 g. (1 mol.) of 4-[(1-ethyl-2(1H)- 8 naphthothiazolylidene)isopropylidene] 3 phenyl-- (4H)-isoxazolone, 3.54 g. (1 mol. plus 200% excess) of 2-ethylmercapto-fi-naphthothiazole ethobromide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 15 ml. of dry pyridine was heated at the refluxing temperature for 30 minutes. After standing at room temperature for 10 minutes, a very small amount of methyl alcohol was added to the reaction mixture and then the dye was collected on a filter and Washed with methyl alcohol. The yield of dye was 12% after two recrystallizations from pyridine. The very dark reddish crystals with a green reflux had melting point 3l4315 C. with decomposition, and they sensitized a photographic gelatino-silverbromoiodide emulsion to about 690 mu with maximum sensitivity at about 665 mu.

,8 naphthothiazolylidene)isopylidene] 2 g. (1 mol. plus 200% excess) of EXAMPLE 4 1,3-diethyl-5 3 ethyl 2(3H) benzo'thinzolylidene) isopropylidene] -2-thi0barbituric acid A mixture of ,134 g. 1 min. of 1,3-diethyl-5-[(3- ethyl 2(3I-I) benzothiazolylidene)isopropylidene] 2- thiobarbituric acid, 2.90 g. (1 mol. plus excess) of 2-I8-acetanilidovinylbenzothiazole methiodide and 0.68 g. (1 mol. plus 100% excess) of triethylamine in 20 ml. of dry pyridine was heated to the boiling point in 40 seconds, kept there for 10 seconds, and then chilled at once. The reaction mixture was stirred with cold water, filtered, and the sticky residue was washed with cold water. The residue became crystalline when it was stirred with methyl alcohol. The crystals were collected on a filter and washed with methyl alcohol. The residue was stirred with acetone, filtered, and the remaining portion washed with acetone. After several such treatments the acetone washings were blue. Then the dye was recrystallized from acetone. The yield of recrystallized dye was 9%. The dark green crystals had melting point 208209 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 690 mu.

EXAMPLE 5 4-[(5 chloro 3 ethyl 2(3H) benz0thiaz0lylidene)- A mixture of 1.98 g. (1 mol.) of 4-[(5-chloro-3-ethyl- 2-(3H)-benzothiazolylidene)isopropylidene] 3 phenyl- 5(4H)-isoxazolone, 1.49 g. (1 mol. plus 100% excess) of p-dimethylaminohenzaldehyde and 1.0 ml. of piperidine were heated together in an oil-bath at -135 C. for 10 minutes. The cool reaction mixture was stirred with ether and then filtered. The residue was stirred with methyl alcohol, the suspension was chilled and then the dye was washed on the filter. with methyl alcohol. The yield of dye Was 50% crude and 30% after two recrystallizations from n-propyl alcohol. decomposed from about C.

EXAMPLE 6 5-[di(3 ethyl 2(3H) benzothiazolylidene)isopropylidene] -1-phenyl-2-{hi0barbituric acid A mixture of 1.41 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene] 1 phenyl 2 thi The dark green crystals obarbituric acid, 3.49 g. (1 mol. plus 200% excess) of 2-ethylmercaptobenzothiazole ethoethylsulfate and 1.01- g. (1 mol. plus 200% excess) of triethylamine in 30 ml. of dry pyridine was heated at the refluxing temperature for 15 minutes. After chilling, the dye was collected on the filter and washed with methyl alcohol. The yield of dye was 39% after two recrystallizations from nitrobenzene. The dark crystals with a green reflex had meltting point above 335 C., and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 645 mu with maximum sensitivity at about 610 mu.

EXAMPLE 7 4- [di (3-methyl-2 (3H -benzthiaz0lylidene isopropylidene] -1-phenyl-5-pyraz0l0ne A mixture of. 2.77 g. [1 mol.) of 3,3'-dimethyl 9- methylmercaptothiacarbocyanine p-toluenesulfonate, 0.80 g. (1 mol.) of l-phenyl-S-pyrazolone and 0.51 g. (1 mol.) of triethylamine in 15 ml. of pyridine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was stirred with 250 ml. of methyl alcohol and then filtered. After washing the residue with methyl alcohol, the remaining portion was extracted with acetone. The dye, which separated on chilling the acetone extract; was recrystallized from acetone. The yield of dye, thus obtained was 24%. The dull reddish needles decomposed from about-175 C., and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 645 mu with maximum sensitivity at about 600 mu.

EXAMPLE 8 A mixture of 1.81 g. (1 mol.) of 3-methyl-4-[(3-rnethyl- 2(3H) benzothiazolylidene)isopropylidene] 1 phenyl- -pyrazolone, 5.50 g. (1 mol. plus 200% excess) of 2-methylmercaptobenzothiazole metho-p-toluenesulfonate and 1.51 g. (1 mol. plus 200% excess) of triethylamine in ml. of dry pyridine was heated at the refluxing temperature for about 15 minutes. After cooling, the reaction mixture was filtered and the residue was washed with methyl alcohol. The filtrate and washings were combined, then concentrated and treated with cold water. The aqueous layer was decanted and the oily residue was treated with successive portions of cold water. Finally the residue was dissolved in benzene and precipitated by adding ligroin (B. P. 90-120 C.). The yield of dye after another such purification was 12%. After another recrystallization from dry benzene, the dull brownish green crystals had melting point 293-294 C. with decomposition, and they sensitized a photographic gelatinosilver-bromoiodicle emulsion to about 650 mu with maximum sensitivity at about 635 mu.

8 EXAMPLE 9 benzothiazolylidene) isopropylidene] -5-pyraz0l0ne the bottom of the beaker. The yield of dye was 35% crude and 18% after one recrystallization from n-propyl alcohol. The very dark purplish crystals had melting point 333--334 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 645 mu with maximum sensitivity at about 595 EXAMPLE 10 3-. E di(3-methyl-2 (3H) -benz-0thiaz0l vlidene) isopropylidnel-Z (3H)-z'midaz0[1,2-al pyridone A mixture of 1.85 g. (Much) of 3,3'-dimethyl-9-methylmercaptothiacarbocyanine p-toluenesulfonate, 1.14 g. (1 mol. plus excess) of 2(3H)-imidazo[1,2-u] pyridone hydrochloride and 0.67 g. (2 mols.) of triethylamine in 25ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After cooling, the dye was collected on a filter and washed with pyridine. The residue was stirred with 300 m1. of boiling pyridine and the suspension was filtered hot. The remaining residue was recrystallized once from n-propyl alcohol and then once from methyl alcohol. The yield of dye, thus obtained, was 43%. The very dark crystals had melting point 242-244 C. with decomposition, and they sensitized a photographic gelatino-silvcr-bromoiodide emulsion to about 670 mu with maximum sensitivity at about 645 mu.

EXAMPLE 11 4-1 (5-chloro-3-ethyl 2 (3H) bcnzothiazolylidene) (3- methyl 2(3H -benz0thiaz0lylidene)isopropylidene]-3- phenyl-S (4H) -isoxazol0rze 5(4H)'-isoxazolone, 1.84 g. (1 mol.) of Z-methylmercaptobenzothiazole metho-p-toluenesulfonate and 0.51 g. (1 mol.) of triethylamine in 50 ml. of dry pyridine was heated at the refluxing temperature for 5 minutes. After cooling, the solid was collected on a filter and washed with methyl alcohol. The residue was stirred, in a beaker, with 100 ml. of hot ethyl alcohol and the suspension was filtered hot. The remaining solid was stirred, in a beaker, with 100 ml. of boiling pyridine. After chilling the suspension, the dye was collected on the filter. The dye was dissolved in 60 ml. of hot nitrobenzene, a few ml. of methyl alcohol was added, and the whole chilled. The yield of dye was 35%. The dull reddish clusters with a greenish reflex decomposed from about 185 C., and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 640 mu with maximum sensitivity at about 615 mu.

EXAMPLE 12 1,3-aiethyl 5 [(3-ezhyl-2 (3H) -benzthiazolylidene) (I- ethyl-Z (1H) quinolylidcne) isopropylidene] -2-thi0bar- A mixture of 1.34 g. (1 mol.) of 1,3-diethyl--[(3- ethyl 2(3H)-benzothiazolylidene)isopropylideneJ-Z-thiobarbituric acid, 3.93 g. (1 mol. plus 200% excess) of 2-phenylmercaptoquinoline ethiodide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 20 ml. of dry pyridine was heated at the refluxing temperature for 15 minutes. After chilling, the reaction mixture was filtered. The filtrate was concentrated and stirred with ice-water and then filtered. The residue was stirred, in a beaker, with hot methyl alcohol. After chilling the suspension, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 59% crude and 38% after two recrystallizations from pyridine. The small dark green and larger brassy crystals had melting point 241- 243 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 705 mu, with maximum sensitivity at about 685 mu.

EXAMPLE l3 1,3-diethyZ-5- (1 ethyl -2 (1H) -}3-naphth0thiazolylidene) (Si-methyl 2(3H)-benzoxazolylidene) isopropylideneJ- 2-thiobarbituric acid 0:0 0 I a l 2 5 II S A mixture of 1.51 g. (1 mol.) of 1,3-diethyl-5-[(1- ethyl-2( lH)-B naphthothiazolylidene)isopropylidenel-Z- thiobarbituric acid, Z-methylmercaptobenzoxazole methop-toluenesulfonate (prepared by heating 1.65 g. of 2- methylmercaptobenzoxazole and 1.86 g. of methyl ptoluenesulfonate together at the temperature of the steam bath for several hours) and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 20 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After cooling, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was crude and 43% after two recrystallizations from pyridine. The green crystals had melting point 294-296 C. with decomposition, and they sensitized a photographic gelatinosilver-bromoiodide emulsion to about 645 mu with maximum sensitivity at about 605 mu.

EXAMPLE 14 1,3-diethyl-5- [di(1-ethyl-2 (1H) -fi-naphth0thiaz0lylidene) isopropylidene] barbituric acid A mixture of 1.45 g. (1 mol.) of 1,3-diethyl-5-[(1- ethyl 2(1H)-fi naphthothiazolylidene)isopropylidenelbarbituric acid, 3.54 g. (1 mol. plus 200% excess) of 2-ethylmercapto-p-naphthothiazole ethobromide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 20 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. A small amount of methyl alcohol was added to the reaction mixture and the whole chilled.-

EXAMPLE l5 2-[di(1 -ethyl-2 (1H) -fl-naphthothiazolylidene) isopropylidene] -1,3-indandione A mixture of 1.32 g. (1 mol.) of 2-[(1-ethyl-2(1H)- fi-naphthothiazolylidene isopropylidene] l ,3 indandione, 3.54 g. (1 mol. plus 200% excess) of 2-ethylmercapto-pnaphthothiazole ethobromide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 20 ml. of dry pyridine was heated at the refluxing temperature for one hour. After cooling to about room temperature, some methyl alcohol was added and then the dye was washed on the filter with methyl alcohol. The residue was extracted with hot pyridine. The pyridine filtrate was concentrated and chilled. The yield of dye was 21% crude and 10% after two recrystallizations from pyridine. The very dark greenish needles had melting point 316-317 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 665 mu with maximum sensitivity at about 630 mu.

Other ketomethylene compounds than those illustrated in the above examples can be employed in the condensation of the meso-substituted carbocyanine dyes of Formula V with the compounds of Formula VI. For example, l,3-di(fi-methoxyethyl)barbituric acid can replace the 2,739,964 12 l-phenyl-S-pyrazolone of Example 7 above, to give the EXAMPLE 17 d d' non ionlze ye having the followlng formula 1,1 di(2 benz0flliaz0lyl) Gr fl benzothiazolylidenemethyl)ethylene (2H, =c 0% (SH: ha. hm CHIOCHECHz-N\ /N-CH2CH2OCH2 s s C y} \C :C/

\g Also, we have found that certain open chain keto- A mixture of 554 (1 mol) f 9;

methylene compounds can l the inter methylmercaptothiacarbocyanine p-toluenesulfonate, 4.23 mediates of Formula V to give non-ionized dyes, some g; (1 mo1+50% excess) of duzhmmmiazelyl)Vmethan of which can be quaternized with alkyl salts, such as the and 2 (2 mol) of triethylamine in 5 ml. f dry f lf p'toluefleslllfonates- Representative of i pyridine was heated at the refluxing temperature for'20 lom y mn y obtamed fr p n hain comminutes. Ice and Water were added to the cold reaction pounds are those of the following general formula: mixture. The dye was collected on a filter and washed VII.

i /S R1 Da /=0 wherein R, R1, n, m, Z and Z1 each have the values with water. The residue was transferred to a beaker and given above and D represents a cyano (CN) group or stirred with hot methyl alcohol. After chilling, the solid a benzothiazolyl group. Examples 16 and 17 below will was collected on a filter and washed with methyl alcohol. serve to illustrate the manner whereby we prepare the The residue was suspended in hot methyl alcohol and the dyes of Formula VII, and Examples 18, 19 and 20 will suspension was filtered hot, and then this operation was serve to illustrate how the dyes of Formula VII can be repeated. The yield of dye was 66% crude and 47% quaternized with an alkyl salt. after two recrystallizations from pyridine. The dull dark green crystals decomposed from about 181 C.

EXAMPLE 16 EXAMPLE 18 1 -(2-bcnzothiazolyl) -1-cyan0- U- fi- (3H) 9- [C'yanOG-methyl-ZUH) -benz0thiaz0lylidene) methyl]- benzothiazolylldenemethyl)ethylene 3,3'-dimethylthiacarb0cyanine p-toluenesulfonate s S S S 50 1 /C=CHC=CHC\ 8 eg N i N (gHa No c o (EH! $11: Ha OSOr-Q'CH:

A mixture of 1.85 g. (1 mol.) of 3,3'- dimethyl-9-meth- N ylmercaptothiacarbocyanine p-toluenesulfonate, 1.74 g. 8 (l mol.+200% excess) of Z-benzothiazolylacetonitrile and 0.67 g. (2 mol.) of triethylamine in 20 ml. of dry pyridine was heated at the refluxing temperature for 30 A mixture of g- B101) 015 ynminutes. Ice and water were added to the cold reaction Yan -2,2-di(3-methyl-2(3H)-benz0thiazolylidenemethmixture. The dye was collected on a filter and washed yl)ethylene and 0.19 g. (1 mol) of methyl p-toluenesul with water. The residue was transferred to a beaker and fonate were fused by heating them togetherover a free stirred with hot methyl alcohol. After chilling, the solid flame and then heating was continued at the temperature was collected on a filter and washed with methyl alcohol. of the steam-bath for three hours. The reaction mixture The residue was suspended in hot methyl alcohol and the Was extracted with hot methyl alcohol. After filteri g, suspension was filtered hot, and then this operation wa the filtrate was concentrated and then chilled. The dye repeated. The yield of dye was 82% crude and 67% was collected on the filter and washed with methylalco' after two recrystallizations from pyridine. The dark red 1101. The yield of dye was 46% after being recrystallized crystals had melting point 249-250" C. with decomposifrom ethyl alcohol. The green crystals had melting point o 218-2l9 C. with decomposition.

l3 EXAMPLE 19 9 [(2-benzothiazolyl) (3-methyl-2 (3H )-benzot hiazolylidene)methyl] -3,3'-dimethylthiacarbocyanine p-toluenesulfonate A'mixture of 1.03 g. (1 mol) of 1,1-di-(2-benzothiazolyl -2,2-di(3-methyl-2(3H)-benzothiazolylidenemethyl)eth- EXAMPLE A mixture of 1.20 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene) isopropylidene] 1 -methyl-2-thiobar'- bituric acid, 3.41 g. (1 mol. plus 200% excess) of 2- methylmercapto B naphthoxazole metho methylsulfate (prepared by heating 2.15 g. of Z-methylmercapto-fl-naph thoxazole and 1.26 g. of methyl sulfate together at the temperature of the steam bath for 24 hours) and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the dye was collected on a filter and washed with pyridine and then methyl alcohol. The yield of dye was 42% crude and 27% after two recrystallizations from n-propyl alcohol. The minute dark reddish crystals with a green reflex had melting point 267269 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 630 mu with maximum sensitivity at about 600 mu.

thiacarbocyanine p-toluenesulfonate A mixture of 1.03 g. (1 mol) of 1,l-di(2-benzothiazolyl-2,2-di 3-methyl-2 3H) -b enzothiazolylidenemethyl) ethylene and 1.24 g. (2 mol+l00% toluenesulfonate was heated in an oil-bath. At the start, the temperature of the oil-bath was 100 C. and the temperature was gradually raised to 125 C. during the heating period of three hours. The reaction mixture was extracted with ether. The remaining portion was extracted with hot methyl alcohol. After filtering, the filtrate was concentrated and then chilled; The dye was collected on a filter and washed with methyl alcohol. The yield of dye was 39% in two crops, after being recrystallized from ethyl alcohol. The green crystals had melting point 325-326" C. with decomposition.

EXAMPLE 21 5 [(3 ethyl 2(3H)-benzothiazolylidene) l-methyl-Z- (1H) fi-naphthoxazolylidene)isopropylidenel-I-methyl-Z-thiobarbituric acid CH: CH;

excess) of methyl p- 5 owl-@423,

EXAMPLE 22 5-[(3-ezhyl-2 (3H) -benzothiazolylidene) (3-ethyl-2 (3H a-naphthothiazolylidene) isopropylidene] -1-methyl- 2 thiobarbituric acid A mixture of 1.20 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene isopropylidene]- 1 -methyl-2-thiobarbituric acid, 4.01 g. (1 mol. plus 200% excess) of 2-ethylmercapto-a-naphthothiazole ethiodide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the solids were collected on a filter and washed with pyridine and then methyl alcohol. The residue was stirred with boiling methyl alcohol and the suspension was filtered hot. The dye was dissolved in hot cresol and ether was added to the filtrate. After graphic gelatino-silver-bromoiodide emulsion to about 670 5 mu with maximum sensitivity at about 630 mu.

EXAMPLE 23 5-[(3-ethyl-2 (3H) -benzthiaz0lylidene) (3-ethyl-4-methylthiazolylidene) isopropylidene1-1-methyl-2-thiobartituric acid A mixture of 1.20 g. (1 mol.) of -[(3-ethyl-2(3H)- benzothiazolylidene) isop ropylidene} l-methyl-Z-thiob arbituric acid, 3.61 g. (1 mol. plus 200% excess) of 4-methyl- 2-phenylmercaptothiazole etho-ethylsulfate (prepared by heating 2.07 g. of 4-methyl-2-phenylmercaptothiazole and 1.54 g. of ethyl sulfate together at the temperature of the steam bath for 24 hours) and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the solid was collected on a filter and washed with methyl alcohol. The concentrated filtrate and washings were stirred with cold water. After chilling, the aqueous layer was decanted, the residue was washed several times with cold Water, and then finally stirred with hot methyl alcohol. After chilling, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 37% after two recrystallizations from pyridine. The bronzy-green crystals had melting point 299-301 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 630 mu with maximum sensitivity at about 590 mu.

EXAMPLE 24 5-[(3-ethyl-2 (3H) -benz0thiaz0lylidene) (1 -ethyl-4 (1 H pyridylidene) is0pr0pylidene1-1 -methyl-2-thi0barbituric acid A mixture of 1.20 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene) is op ropylidene]- 1-methyl-2-thiob arbituric acid, 3.43 g. (1 mol. plus 200% excess) of 4-phenylmercaptopyridine ethiodide and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the solids were collected on the filter and washed with methyl alcohol. The concentrated filtrate and washings were stirred with cold water. After chilling, the aqueous layer was decanted and the sticky residue was stirred with successive portions of water, and then finally stirred with hot methyl alcohol. After chilling, the dye was collected on a filter and washed with methyl. alcohol. The yield of dye was 4% after two recrystallizations from pyridine. The very dark crystals had melting point 240-241" C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emul- 16 sion to about 650 mu with maximum sensitivity at about 600 mu. I

EXAMPLE 25 5-[(3-ethyl-2 (3H) -benzothiaz0lylidene) (1-ethyl-4(1H)- quinolylidene)is0p1'0pylidene]-1-methyl-2-thiobarbituric acid c=on-o=onv airs-021i; N/ 9 5 A mixture of 1.20 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene] 1 methyl 2 -.thiobarbituric acid, 4.37 g. (1 mol; plus 200% excess) of 4- phenylmercaptoquinoline etho p toluenesulfonate and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 m1. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the dye was collected on a filter and washed with pyridine and then methyl alcohol. The yield of dye was 68% crude and 59% after two recrystallizations from pyridine. The blue-green crystals had melting point 227-22810 with decomposition, and they sensitized a photographic gelatino-silverbromoiodide emulsion from about 600 mu to 735 mu with maximum sensitivity at about 700 mu.

EXAMPLE 26 1 ethyl 3-[di(3 ethyl 2(3H) benz0tkiaz0lylidene)- isopropylidenel-Z-thio-oxindole S S A mixture of 2.45 g. (1 mol.) of 3,3-diethyl-9-methyl'v mercaptothiacarbocyanine bromide, 1.77 g. (1 mol. plus excess) of 1-ethyl-2-thio-oxindo1e and 0.51 g. (1 mol.) of triethylamine in25 ml. of dry-pyridinewas-heated at the refluxing temperature for five minutes. After chilling, the solids were collected on the filter and washed with methyl alcohol. The residue was extractedwith successive portions of hot methyl alcohol. The yield of dye was 11% after two recrystalizations from pyridine. The minute reddish-purple crystals had melting point 279- 282 C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 630 mu with maximum sensitivity at about 600 mu.

EXAMPLE 27 5 [(5 chloro 1,3 diethyl 2(3H) benzimiddzolyli A mixture of 1.20 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene] 1 methyl 2 thiobarbituric acid, 3.95 g. (1 mol. plus. 200% excess) of 5- chloro l ethyl 2 ethylmercaptobenzimidazole etho-ethylsulfate (prepared by heating 2.41 g. of 5-chloro- 1-ethyl-2-ethylmercaptobenzimidazole and 1.54 g. of ethyl sulfate together at the temperature of the steam bath for 24 hours) and 1.01 g. (1 mol. plus 200% excess) of triethylamine in 25 ml. of dry pyridine was heated at the refluxing temperature for 20 minutes. After chilling, the solid was collected on a filter and washed with methyl alcohol. The concentrated filtrate and washings were stirred with cold water. After chilling, the aqueous layer was decanted and the oily residue was stirred with several successive portions of cold water. The oily portion was stirred with hot methyl alcohol. After chilling and filtering, the filtrate was concentrated. The oily residue was stirred with ligroin B. P. 90-120" C.) and the ligroin layer was decanted. The residue was recrystallized from ethyl acetate. The reddish crystals decomposed from about 185 C., andthey sensitized aphotographic gelatinosilver-bromoiodide"emulsion to about 570 mu with maximum sensitivity at about 5 30 mu.

EXAMPLE 28 A mixture of 1.00 g. (1 mol.) of l,3-diethyl-5-[(3-ethyl'- 2(3H) benzothiazolylidene)isopropylidene] 2 thiobarbituric acid, 2.32 g. (1 mol. plus 100% excess) of 2- methylmercapto-;8-naphthoselenazole metho- -toluenesulfonate and 0.51 g. (1 mol. plus 100% excess) of triethylamine in 15 ml. of dry' pyridine was heated at the refluxing temperature for five minutes. After chilling, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 89% crude and 40% after tworecrystallizations from pyridine. The green crystals had melting point above 340 C., and they sensitized a photographic gelatino-silver-bromoiodide' emulsion from about 540 mu to about 680 mu with maximum sensitivity'at about 660 mu.

EXAMPLE 29 5 [I ethyl 2(1H) 13 naphthothiazolylide'ne) (1,3,3 trimethyl 2(IH)' indblylidene)isopropylidene] 1 methyl-2-tliiobafbituric acid thiobarbituric acid, 3.99 g. (1 mol. plus 200% excess) of 2 ethylmercapto- B naphthothiazole etho' ethyl sulfate and 1.01 g. (1 mol. plus 200% excess) of triethyla mine in 25 ml. ofdry pyridine was heatedat'therefiuxing After chilling, the dye was temperature for 20 minutes collected on-a filter: and washedwith pyridine. The dye was extracted with hot n-propyl alcohol and thenthe resi-- due was recrystallized frompyridine; The green and cop- 18 pery green: crystals had melting point 260-261 C. with decomposition, and they sensitized a photographic gelat ino-silver-bromoiodide emulsion to about 635 mu with mercapto-4,5,4,5-dibenzothiacarbocyanine1 eth'ylsulfate,

1.18 g. (1 mol. plus excess) ,of- 3-ethyl-4-thiorhodanine and 0.37 g. (1 mol. plus 10% excess) of triethylamine in 35 ml. of anhydrous ethyl alcohol was heated at the refluxing temperature for 15 minutes. After chilling, the; solid was collected on a filterand washed with methyl alcohol. The residue was dissolved in hot pyridine: After chilling, the crystals were collected on a filteil The filtrate was concentrated. Aft'e'r chilling the crystals were collected on a'filter and washed with methyl alcohol, and then recrystallized by dissolving' them in hot pyridine and adding methyl alcohol to the v filtrate. The" yield of dye, thus obtained, was 24%. The dark purplish crystals had melting point 260-261" C. with decomposition, andthey sensitized a photographic gelatinosilver-bromoiodide emulsion from about 550 mu to about 720 mu with maximum sensitivity at about 690 mu.

EXAMPLE 31 Amixture' of 1.31 g.' (1 mol.) of 5' -[(5 -chloro'-3-ethyl 2'(3I- I) 7 benzothiazolylidene)isopropylidene}1-methyl-2-, thidbarbitllric acid, 3.86 1 mol. I I 5-chloro-2 ethylmercaptobenzothiazole ethio dide and 1.01

g. (1- mol. plu's'200% excess) of trieth'ylamine in 20ml.-

5 [(3 ethyl" 2(3H') benzoselenazolylidertje) (3 ethyl- 2 (3H) behzothiazolyliderie) is0pr0pyliden'e]-1-methyl- Z-thiobarbiiufic acid plus 200% excess), olf- A mixture of 1.01 g. (1 mol.) of -[(3-ethyl-2(3H)- benzoselenazolylidene)isopropylidene] 1 methyl-Z-thiobarbituric acid, 2.62 g. (1 mol. plus 200% excess) of 2- ethylmercaptobenzothiazole etho-ethylsulfate and 0.76 g. (1 mol. plus 200% excess) of triethylamine in ml. of dry pyridine was heated at the refluxing temperature for 15 minutes. After chilling, the solids were collected on a filter and washed with pyridine and then with methyl alcohol. The concentrated filtrate and washings were stirred with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was transferred to a beaker and stirred with boiling methyl alcohol. After chilling, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 27% after two recrystallizations from pyridine. The dull dark green crystals had melting point above 300 C., and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about 650 mu with maximum sensitivity at about 625 mu.

EXAMPLE 33 5 [di(1 -ethyl-2 1H -B-naphthothiazolylidene) isopropy Iidenel-I ,3-di (fl-methoxyethyl) barbituric acid A mixture of 2.48 g. (1 mol.) of 5-[(l-ethyl-2( 1H) 4'?- naphthothiazolylidene)isopropylidene1-1,S-di (fi-methoxyethyl)barbituric acid, 3.99 g. (1 mol. plus 100% excess) of 2-ethylmercapto-B-naphthothiazole etho-ethylsulfate, 15 ml. of isoquinoline and 1.01 g. (1 mol. plus 100% excess) of triethylamine was heated in an oil bath at 165169 C. for one hour. The cool reaction mixture was filtered, the residue was washed with a little methyl alcohol. The combined isoquinoline filtrate and alcoholic washings were treated with about 300 ml. of ether. The chilled mixture was filtered, and the residue was washed with ether. The residue was transferred to a beaker and treated with hot methyl alcohol. After chilling, the dye was collected on a filter and washed with methyl alcohol. The dye was purified by dissolving it in hot pyridine, filtering the solution and adding hot methyl alcohol to the hot pyridine filtrate. The yield of purified dye was 22%. The bronze-green crystals melted at 307308 C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 670 mu.

EXAMPLE 34 5-[(di(1-ethyl-2 (1H) -B-naphthothiazolyiidene) isopropylidene1-1-n-heptylbarbituric acid 20 mercapto-fl-naphthothiazole etho-ethylsultate, 15 ml. of isoquinoline and 1.01 g. (1 mol. plus excess) of triethylamine was heated in an oil bath at -170" C. for one hour. The dye was isolated and purified in the same manner as given in the previous example. The yield of purified dye was 15%. The dull green crystals melted at 296-297 C. with decomposition, and they sensitized a photographic gelatiuo-silver-hromoiodide emulsion with maximum sensitivity at about 660 mu.

EXAMPLE 3S N $5115 O=C CHaO CHaCHq-N\ A mixture of 2.48 g.-(l mol.) of 5-[(1-ethyl-2-(ll-I)- 5 naphthothiazolylidene)isopropylidenel-l,3-di(;9-methoxyethyl)barbituric acid, 4.17 g. (1 mol. plus 100% excess) of Z-methylmercapto-,B-naphthothiazole inetho-ptoluenesulfonate, 35 ml. of pyridine and 1.01 g. (1 mol. plus 100% excess) of triethylamine was heated at the refluxing temperature for 30 minutes. After cooling, the dye was collected on a filter and washed with methyl alcohol. The dye was suspended in hot methyl alcohol and filtered. The yield of dye was 70% crude and 52% after two recrystallizations from pyridine. The melting point of the brassy-green crystals was above 320 C. and the dye sensitized a photographic gelatino-silvcr-bromoiodide emulsion with maximum sensitivity at about 655 mu.

/N-C HQCHIO CH1 EXAMPLE 36 5-[ (1 ethyl-2 (1H)-B-naphthothiaz0lylidene) (1 methyl- 2 (1H) 8 naph thothiazolylidene) isopropylidenel-l -ni2eptyl-3-phenylbarbituric acid A mixture of 1.11 g. of 5-[(l-ethyl-2(lH)-5-napl1thothiazolylidene)isopropylidene]-1-n-heptyl 3 phenylbarbituric acid, 1.67 g. (1 mol. plus 100% excess) of 2- methylmercapto-flmaphthothiazole metho-p-toluenesulfonate, 35 ml. of pyridine and 0.41 g. (1 mol. plus 100% excess) of triethylamine was heated at the refluxing temperature for 30 minutes. The cool reaction mixture was filtered. The residue was suspended in three successive portions of hot benzene and each hot suspension was filtered. The yield of dye after two recrystallizations from pyridine was 33%. The melting point of the green crystals was above 320 C. and the dye sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 665 mu.

. .2 EXAMPLE 37 1-ezhyl-5- [di(1-ethyl-2 (1H,) -fi-naph'thothiazolylidene.) isopropylidene] barbituric acid Amixture of 1.36 g. (1 mol.) of 1-ethyl-5- [(.l -ethyl- 2( 1H) -p-naphthothiazolylidene)isopropylidene] barbituric acid, 3.54 g. (1 mol. plus 200% excess) of 2-ethylmercapto-B-naphthothiazole ethobromide, 20 'ml. of dry pyridine and 1.01 g. (1 mol. plus 200% excess) of triethylamine was heated at the refluxing temperature for 20 minutes. The cold reaction mixture was filtered and the residue was washed with pyridine. The residue was extracted with some warm pyridine. The pyridine filtrate, washings and extract were combined, concentrated and then treated with cold water. After chilling, the aqueous pyridine was removed, the residue was treated with hot methyl alcohol and the suspension was filtered. The dye was given three recrystallizations from pyridine. The melting point of the shiny green crystals was above 330 C. and this dye sensitized a photographic gelatino-s'ilve'rbromoiodide emulsion with maximum sensitivity at about 630 mu.

EXAMPLE 38 1,3 diethyl 5 [di(1 ethyl-2(1H)-fi-naphthothiaz0lylidene) isopropylidene] -.2-.thiobarfbituric acid A mixture of 1.50 g. .(1 mol.) of .1,3-diethyl-5-[(lethyl 2(1H)-,8-naphthothiazolylidene)isopropylidene] 2- thiobarbituric acid, 3.54 g. (1 mol. plus 200% excess) of 2-ethylmercapto-B-naphthothiazole ethobr'ornide, ml. of pyridine and 1.01 g. (1 mol. plus 200% excess) of triet'hylamine was heated at the refiuxingtemperature for minutes. The cool reaction mixture was filtered and the residue was washed witha little pyridine. The residue was extracted with pyridine and then twice recrystailized from pyridine. The yield of purified dye was 19%. The yellowish-green crystals melted at 309-310" C. with decomposition, and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about '665 mu.

EXAMPLE 39 5 22 A mixture of 1'.24 g: (1 mol.) of 5--[.('1-ethyl-2( 1H) 131- naphthothiazolylidene) isopropylidene] -1,3-di (fl-methoxw ethyl) barbituric acid, 2.32 g.(:1 mol. plus 100% excess) of Z-methylmercaptofimaphthoselenazole metho -tolu- 5 enesulfonate', 25- ml. of dry pyridine and 0.51 g. (1 mol.

plus 100% excess) of triethylamine was heated at the refiuxing temperature for 10 minutes. The cool reaction mixture was filtered, the residue treated with hot methyl alcohol and the suspension was filtered. The yield of dye 10 was 93% 317318 C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsionwith maximum sensitivity at about 665 mu.

EXAMPLE 40 5- 1-ethyl-2 1H) -fi-naph thothiazolylidene) (3 methyl- 2 (3H) -zx-naph thoxazolylidene) isopropylidene] 1,3-di- (/3-melh0xyethyl) barbituric acid lh-CEHzCHzO'CHI A mixture of. 2.48 g. (1 mol.) of 5-[(1'ethyl-2(1H)- B naphthothiazolylidene)isopropylidene] 1.3 diQS- methoxyethyl) barbituric acid, 4.01 g. (1 mol. plus 100% excess) of Z-methylmercapto-a naphthoxazole metho-ptoluenesulfonate (prepared by heating 2.15 g. of2-methylmercapto-a-naphthoxazole and 1.86 g. of methyl p-toluenesul'fonate together at the temperature of the steam bath for 5 hours), 20 ml. of isoquinoline and 1.01 g. :(1 mol. plus 100% excess) of triethylamine was heated in an oil bath at 160-170 'C. for -67 minutes. The cool reaction mixture was filtered and the residue was washed with a little methyl alcohol. "Thelcom'bined filtrate and washings were treated with ether. After chilling, the ether layer was decanted and the residue was washed with ether. The residue was treated with hot methyl alcohol. After chilling, the suspension was filtered. The yield of dye was 12% after two recrystallizations from pyridine. The dark-red crystals with a green reflux melted at 302- 303 C. with decomposition and they sensitized a photographic gelatino-silver bromoiodide emulsion with maximum sensitivity at about 610 mu.

idene') (1 -methyl-2 (1H )-}3-naphthoxaz0lylidene) .is0- propylidene] barbituric acid mixture of 2.18

barhituric acid, 4.01 "g. (-1 mol. plus excess)-of 2- methylmercapto-p-naphthoxazole vmetho-p-toluenesufiocrude and 77% after two recrystallizations from pyridine. The brassy-green crystals melted at' g. (.1 mol.) of 1,3-diethyl-'5-lI-('1- ethyl- 2(1H) pnaphthothiazolylidene) isopr'opylidene]-- together at the temperature of the steam bath for about 18 EXAMPLE 42 1,3 diethyl 5.- [(1 ethyl 2(1H) g8 naphthothiazolylidene) (3 ethyl 2(3H) a naphthothiazolylidene) isopropylidene] barbituric acid A mixture of 2.18 g. (1 mol.) of 1,3-diethyl-5-[(1-ethyl- 2(1H) 3 naphthothiazolylidene)isopropylidenelbarhituric acid, 4.01 g. (1 mol. plus 100% excess) of Z-ethylmercapto-a-naphthothiazole ethiodide, 25 ml. of isoquinoline and 1.01 g. (1 mol. plus 100% excess) of triethylamine was heated in an oil bath at 162166 C. for one hour. The dye was isolated and purified in the same mannor as given in the previous example. The yield of dye was 2% after two recrystallizations from pyridine. The melting point oi the dark-green crystals was above 325 C; and the dye sensitized a photographic gelatino-silverbromoiodide emulsion with maximum sensitivity at about 655 mu.

EXAMPLE 43 5, tans ethyl -.2(3H) benzothiazolylidene)isopropylidenel rhodanine A mixture of 1.10 g. (1 mol.) of 3,3-diethyl-9-ethylmercaptothiacarbocyanine iodide, 1.33 g. (1 mol. plus 400% excess) of rhodanine, 15 ml. of pyridine and 0.40

- g. of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the solid was collected on a filter and washed with water. ferred to a beaker, treated with hot methyl alcohol and after chilling the suspension, the dye was collected on a filter and washed with methyl alcohol. The dye was dissolved in hot pyridine, the solution was filtered and hot methyl alcohol was added to the hot pyridine filtrate. After chilling, the solid was collected on a filter and washed with methyl alcohol. After another such purification the yield of dye was 66%. The dark-green crystals melted at 277278 C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 620 mu.

Ina like manner 3allyl-5-[di(3-ethyl-2(3H) -benzothia- 'zolylidene)isopropylidenelrhodanine was prepared by using 1.73 g. of 3-allylrhodanine in place of the 1.33 g.

. of rhodanine. .The yield of purified dye was 60%. The

The residue was trans-.

green crystals melted at 228-230 C. with decomposition and theysensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 615 In a similar manner 3-ethyl-5-[di(3-ethyl-2(3H) -benzothiazolylidene)isopropylidenelrhodanine was prepared by fluxing temperature for 20 minutes.

using 1.61 g. of 3-ethylrhodanine-in place of the 1.33 g. of rhodanine. The yield of purified dye was 73%. The green crystals melted at 261-262" C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 615 EXAMPLE 44 l,l-dicytznO-Z,2-di(3-ethyl 2(3H)-benz0thiazolylidenei methybethylene A mixture of 1.38 g. (1 mol.) of 3,3'-diethyl-9-ethylmercaptothiacarbocyanine iodide, 0.66 g. (1 mol. plus 300%, excess) of-malononitrile, 20 ml. of dry pyridine and 0.51 g. of triethylamine was heated at the refluxing temperature for 20 minutes. After chilling, the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 89% crude and 68% after two recrystallizations from npropyl alcohol. The orange-red crystals melted at 272-273 C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion to about590 mu.

V EXAMPLE 45 1 benzoyH-cyan0-2,2-di(3-ethyl-2 (3H) benzothiozolylidenemethyhethylene A mixture of 1.38 g. (1 mol.) of 3,3'-diethyl-9-ethylmercaptothiacarbocyanine iodide,- 1.34 g. (1 mol. plus 300% excess) of benzoylacetonitrile, 20 ml. of dry pyridine and 0.51 g. of 'triethylamine was heated at the re- The cold reaction mixture was treated with cold water and after chilling, the solid was collected on a filter and washed with water. The residue was treated with a little hot methyl alcohol. After chilling, the dye was collected on a' filter and washed with cold methyl alcohol; The yield of dye was 24% crude and 12% after two recrystallizations from n-propyl alcohol. The-dark-brownish crystals melted at 253254 C. with decomposition and they s'ensitized a photographic gelatino-silver-bromoiodide emulsion to about 630 mu.

EXAMjPiLE 46 1 (2-:'1enzofr4r0yl mystic-2,2415(3-ethyI-2 (3H) benzothiazolylidenem'ethyl) ethylene A mixture of 1.29 g. (1 mol.) of 2-{[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidenelcyano acetyl} benzofuran, 3.49 g. (1 mol. plus 200% excess) of Z-ethylmercaptobenzothiazole etho-ethylsulfate, 20 ml. of pyridine and 1.01 g. (1 mol. plus 200% excess) of triethylamine was heated at the refluxing temperature for 20 minutes. The cooled reaction mixture was filtered and the filtrate was treated with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was transferred to a beaker, stirred with hot methyl alcohol, the suspension was chilled and the dye was washed on the filter with methyl alcohol. The yield of purified dye, recrystallized from n-propyl alcohol, was 8% The very dark crystals melted at 26l262 C. with decomposition and they sensitized a photographic gelatinosilver-bromoiodide emulsion to about 650 mu with maximum sensitivity at about 620 mu.

EXAMPLE 47 A mixture of 1.10 g. (1 mol.) of 5-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene]barbituric acid, 6.98 g. (1 mol. plus 500% excess) of 2-ethylmercaptobenzothiazole etho-ethylsulfate, 25 ml. of dry pyridine and 2.02 g. (1 mol. plus 500% excess) of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was filtered. The residue was extracted with 400 ml. of n-propyl alcohol. This extract was concentrated to about 100 ml. and filtered hot. The dye which separated from this chilled concentrated solution was recrystallized from n-propyl alcohol. The yield of dye was 4%. The melting point of the dark-red crystals was above 330 C. and the dye sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 590 mu.

EXAMPLE 48 3- [di (3-methyl 2 (3H) benzothz'azolylz'dene) isopropylidene] -8-methyl-2 (3H -imidaz0 [1,2-mlpyridone A mixture of 1.85 g. (1 mol.) of 3,3'-dimethyl-9- methyl-mercaptothiacarbocyanine'p-toluenesulfonate, 1.23 g. (1 mol. plus 100% excess) of 8-methyl-2(3H)-imidazo[1,2-a]pyridone hydrochloride, 25 ml. of dry pyridine and 0.67 g. of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was washed with ether and then extracted with benzene. The yield of dye was 92% crude and 35% after two recrystallizations from methyl alcohol. The dark-green crystals melted at 239-241" C. with decomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 640 mu.

26 EXAMPLE 49 1 A mixture of 1.38 g. (1 mol.) of 3,3"-diethyl-9.et-hylmercaptothiacarbocyanine iodide, 2.44 g. (1 mol. plus 300% excess) of 5,7-dioxo-3-phenyl-6,7-dihydro-5-thiazolo[3,2-a]pyrimidine, 20 ml. of dry pyridine of 0.51 g. of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was'treated with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was transferred to a beaker, stirred with hot methyl alcohol, the suspension was chilled and the dye was washed on the filter with methyl alcohol. The yield of purified dye, recrystallized from n-propyl alcohol, was 7% The brassy-green crystals melted at 234-236 C. withxdecomposition and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 585 mu.

EXAMPLE so A 4- [di 3-ethyl-2 3H) -Z enz0thiaz0lyliden.e) isopropyli dene]-11phenyl15-pyraz0lone A mixture of 1.10 g. (1 mol.) of 3,3"-diethyl-9-ethylmercaptothiacarbocyanine iodide, 1.60 g. (1 mol. plus 400% excess) of l-phenyl-S-pyrazdlone, 15 ml. of dry pyridine and 0.40 g. of triethylamine was heated at the EXAMPLE s1 3-ezhyl-5- [di(3-ethy l-2'(3H) -benzothiaz0lylidene.) isopropylidene] -2-thi0-2,4-oxazolidinedione A mixture of 1.10 g. (J; mol.) of 3,'3'-.diethyI-9-ethylmercaptothiacarbocyanine iodide, 1.45 g. (1 mol. plus 400% excess) of 3-ethyl-2-thio-2,4-oxazolidinedione, 15 m1. of dry pyridine and 0.40 g. of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the aqueous layer was decanted, the residue was dissolved in methyl alcohol and cold water was added. Again chilled, and the aqueous layer decanted. The residue was stirred with benzene, chilled. The dye was then dissolved in a very little pyridine, the solution was filtered and methyl alcohol was added to the pyridine filtrate. The yield of purified dye was 46%. The dark-reddish crystals decomposed from about 190 C. and they sensitized a photographic gelatino-silver-bromoiodide emulsion with maximum sensitivity at about 5 80 mu.

EXAMPLE 52 2- [di(3-ethyl-3 (2H) -benzothiazlylidene) isopropylidene1-3 (2H) -thianaphthenone A mixture of 1.10 g. (1 mol.) of 3,3-diethyl-9-ethy1- mercaptothiacarbocyanine iodide, 1.50 g. (1 mol. plus 400% excess) of 3(2H)-thianaphthenone, 15 ml. of pyridine and 0.40 g. of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was transferred to a beaker, stirred with hot methyl alcohol, the suspension was chilled and the dye washed on a filter with methyl alcohol. The dye was dissolved in hot pyridine, the solution was filtered and hot methyl alcohol was added to the hot pyridine filtrate. After chilling, the dye was collected on a filter and washed with methyl alcohol. After another such treatment the yield of dye was 43%. The coppery mat of crystals melted at 220222 C. with decomposition and thedye sensitized a photographic gelatino-silver-bromoiodide emulsion with maxima sensitivity at about 520 mu and 600 mu.

EXAMPLE s3 3-ethyl-4-ldi(3-ethyl-2 (3H)-benzothiazolylidene) isopropylidene] -2-thi0-2,5-thiaz0lidinedione CQHFN (3-10 A mixture of 0.90 g. (1 mol.) of 3-ethyl-4-[(3-ethyl- 2(3H)-benzothiazolylidene)isopropylidenel 2 thio-2,5- thiazolidinedione, 1.75 g. (1 mol. plus 100% excess) of 2- ethylmercaptobenzothiazole etho-ethylsulfate, 15 ml. of dry pyridine and 0.51 g. (1 mol. plus 100% excess) of triethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the solid was collected on a filter and washed with water. The residue was transferred to a beaker, stirred with hot methyl alcohol, the suspension was chilled and the dye was washed on the filter with methyl alcohol. The yield of purified dye, recrystallized from n-propyl alcohol, was 37%. The dull dark-green crystals melted at 292294 C. with decomposition and they sensitized a photographic gelatino-silverbromoiodide emulsion with maximum sensitivity at about 580 mu.

28 EXAMPLE 54 5 [di (5-chloro-3-ethyl-2 (3H )-benzothiazolylidene) isopr0pylidene]1,3-di(fl-methoxyethyl)barbituric acid o i l A mixture of 2.40 g. (1 mol.) of 5-[(5-chloro-3-ethyl- 2(3H) benzothiazolylidene) isopropylidene] 1,3 di(pmethoxyethyl)-barbituric acid, 3.39 g. (1 mol. plus 100% excess) of 5-ch1oro-2-ethylmercaptobenzothiazole ethobromide, 20 ml. of dry pyridineand 1.01 g. (1 mol. plus 100% excess) of trlethylamine was heated at the refluxing temperature for 20 minutes. The cool reaction mixture was treated with cold water. After chilling, the aqueous layer was decanted, the oily layer was stirred with cold water, the aqueous layer was decanted and the residue dissolved in hot benzene. After chilling, the dye was collected on a filter and washed with benzene. The yield of dye was 2% after two recrystallizations from benzene. The purplish crystals melted at 282-283 C. with decomposition and they sensitized a photographic gelatino-silverbrornoiodide emulsion with maximum sensitivity at about 590 mu.

EXAMPLE 55 A mixture of 1.93 g. (1 mol.) of 1,3-diethy1-S -[(5-' ethyl-2(3H) benzothiazolylidene)isopropylidene] barbituric acid, 2.25 g. (1 mol.) of Z-B-acetanilidovinylbenzothiazole ethiodide, 25 ml. of nitrobenzene and 1.01 g. of triethylarnine was heated at about 98 C. for 20 minutes. The cool reaction mixture was treated with methyl alcohol. After chilling and filtering, the residue was washed with a little methylalcohol. The combined filtrate and washings were concentrated; The residue was stirred with petroleum ether. The upper layer was decanted, the sticky residue was stirred with successive portions of petroleum ether, ligroin (B. P. -120 C.) and water. The yield of purified dye, recrystallized from methyl alcohol, was 8%. The green crystals decomposed from about 189 C. and they sensitized a photographic. gelatinosilver-bromoiodide emulsion with maximum sensitivity at about 700 mu.

EXAMPLE 5 6 Ca -g1) C-O A mixture of 1.81 g. (1 mol.) of 4-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene] 3 phenyl 5,(4H)- isoxazolone, 2.25 g. (1 mol.) of Z-B-acetanilidovinylbenzothiazole ethiodide, 25 ml. of nitrobenzene and 1.01 g. of triethylamine was heated at 95-100 C. for 30 minutes. A little methyl alcohol was added to the cool reaction mixture and then ether was added. After chilling, the ethernitrobenzene-methyl alcohol layer was decanted. The residue was stirred with ether and the ether extract was added to the other liquid portion. The whole was concentrated, the residue was stirred with petroleum ether and the liquid portion was decanted, the residue was stirred with ligroin (B. P. 90-120 C.) and the ligroin layer decanted, then the residue was stirred with benzene and the benzene layer decanted, then the residue was stirred with ethylacetate and the ethylacetate layer decanted and finally the residue was dissolved in methyl alcohol. The yield of dye after another recrystallization from methyl alcohol was 1%. The dye was obtained as coppery crystals.

EXAMPLE 57 2-[ (3 ethyl-2 (3H )-benz'othiazolylidene) (3-ethyl-2 (3H) benzothiazolylidene ethylidene)isopropylidene] 1,3 ina'andione A mixture of 1.73 g. (1 mol.) of 2-[(3-ethyl-2(3H)- benzothiazolylidene)isopropylidene]-l,3-indandione, 2.25 g. (1 mol.) of 2- -acetanilidovinylbenzothiazole ethiodide, 25 ml. of nitrobenzene and 1.01 g. of triethylamine was heated at about 95 C. for 20 minutes. A little methyl alcohol was added to the cool reaction mixture and the whole was chilled, filtered and the residue was washed with a little methyl alcohol. The combined filtrate and washings were stirred with ether. After chilling, the solid was collected on a filter. The ether-methyl alcohol-nitrobenzene filtrate was concentrated and the residue was stirred with petroleum ether. After chilling, the upper layer was decanted and the sticky residue was washed with three successive portions of ligroin (B. P. 90-120" C.). The residue was stirred with hot benzene and filtered. The residue was stirred with two portions of hot ethyl acetate. The remaining residue was stirred With hot methyl alcohol, filtered and the filtrate chilled. The dye was then recrystallized from n-propylalcohol. The green crystals melted at 271272 C. with decomposition.

EXAMPLE 5 8 3- (3-ethyl-2 (3H) benzothiazolylidene) (3-ethyl-2 (3H) benzothiazolylidene-ethylidene) isopropylidene] -2 (3H) imidazo [1,2-a1pyrid0ne 30 A mixture of 1.68 g. (1 mol.) of 3-[(3-ethyl-2(3H)- benzothiazolylidene) isopropylidene] '2 3H) -imidazo[ 1 2-alpyridone, 2.25 g. (1 mol.) of 2- 6-acetanilidovinylbenzothiazole ethiodide, 25 ml. of nitrobenzene and 1.01 g. of triethylamine was heated at about 97 C. for 20 minutes. The cool reaction mixture was stirred with a little methyl alcohol and more ether. After chilling, the upper layer was decanted and the residue was washed with ether and then water. The residue was stirred with methyl alcohol, chilled and'the suspension was filtered. The residue was stirred with hot benzene and the suspension was filtered hot. The residue was stirred with methyl alcohol and the suspension was filtered. The remaining residue was recrystallized from methyl alcohol. The yield of purified dye was 7%. The green crystals melted at 214-215 C. with decomposition and they sensitized a photographic gelatino-silver bromoiodide emulsion with maximum sensitivity at about 710 mu.

In the preparation of photographic emulsions containing our new non-ionized dyes, it is only necessary to disperse the dyes in the emulsions. The methods of incorporating dyes in emulsions are simple and well known to those skilled in the art. It is convenient to add the dyes from solutions in appropriate solvents. Methanol, pyridine, etc., alone or in admixture, have proved satisfactory as solvents for many of our new dyes. A mixture of pyridine and acetone can be used where the solubility of the dyes in methanol is lower than desired. In several instances, aside from its solubilizing effect, pyridine also has a beneficial effect on the sensitizing action of the dyes.

Sensitization by means of our dyes is, of course, directed primarily to the ordinarily employed gelatino-silver-halide developing-out emulsions. The dyes are advantageously incorporated in the washed, finished emulsions and should, of course, be uniformly distributed throughout the emulsions.

The concentration of our dyes in the emulsion can vary widely, i. e., from about 5 to about 100 mgs. per liter of flowable emulsion. The concentration of the dye will vary according to the type of light-sensitive material in the emulsion and according to the effects desired. The suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art upon making the ordinary tests and observations customarily usedin the art of emulsion making.

To prepare. a gelatino-silver-halide emulsion sensitized with one of our dyes, the following procedure is satisfactory: A quantity of the dye is dissolved in methyl alcohol or other suitable solvent and a volume of this solution containing from 5 to 100 mgs. of dye is slowly added to about 1000 cc. of a gelatino-silver-halide emulsion, with stirring. Stirring is continued until the dye is uniformly distributed throughout the emulsion. With most of our dyes, 10 to 20 mgs. of dye per liter of emulsion sufiices to produce the maximum sensitizing eifect with the ordinary gelatino-silver-bromide (including bromiodide) emulsions. With fine-grain emulsions, which include most of the ordinarily employed gelatino-silver-chloride emulsions, somewhat larger concentrations of dye may be necessary to secure the optimum sensitizing effect.

The above statements are only illustrative and are not to be understood as limiting our invention in any sense, as it will be apparent that our dyes can be incorporated by other methods in many of the photographic silver halide emulsions customarily employed in the art. For instance, the dyes may be incorporated by bathing a plate or film upon which an emulsion has been coated, in the solution of the dye, in an appropriate solvent. Bathing methods, however, are not to be preferred ordinarily.

What we claim as our invention and desire to secure by Letters Patent of the United States is:

1. A non-ionizedcyanine dye selected from those represented by thefollowing general formula:

wherein R and R1 each represents an alkyl group, Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, A represents a member selected from the group consisting of an oxygen atom and a sulfur atom, n, m, and d each represents a positive integer of from 1 to 2, and Z and Z each represents the nonmetallic atoms necessary to complete a nucleus selected from the group consisting of those of the indandione series and a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring.

2. A non-ionized cyanine dye selected from those represented by the following general formula:

wherein R, R1, R, and R each represents an alkyl group.

4. A non-ionized eyanine dye selected from those represented by the following general formula:

wherein R, R1, R, and R" each represents an alkyl group.

5. A non-ionized cyanine dye selected from those represented by the following general formula:

wherein R, R1, R, and R" each represents an alkyl group.

6. A non-ionized dye selected from those represented by the following general formula:

wherein R, R1, R, and R" each represents an alkyl group. 7. The non-ionized cyanine dye having the following formula:

8. The non-ionized cyanine dye having the following formula:

9. The non-ionized eyanine dye having the following formula:

10. The non-ionized cyanine dye having the following formula:

11. The non-ionized cyanine dye having the following formula:

ll 12. A process for making non-ionized cyanine dyes comprising condensing a merocarbocyanine dye selected from those represented by the following general formula:

011 /Q\ R1 T( CH=OH),. C=OH(l3=6 b-A wherein R represents an alkyl group, A represents a member selected from the group consisting of an oxygen atom and a sulfur atom, n represents a positive integer of from 1 to 2, and Q and Z each represents the non- 34 metallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring, with a cyclammonium quaternary salt selected from those represented by the following general formula:

References Cited in the file of this patent UNITED STATES PATENTS 2,385,815 Kendall Aug. 21, 1941 

1. A NON-IONIZED CYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 